Methods of controlling insects

ABSTRACT

The present invention provides methods comprising applying to a crop of rice plants, the locus thereof, or propagation material thereof, a compound of formula (I): wherein —B 1 —B 2 —B 3 — is —C═N—O—, —C═N—CH 2 —, —C═CH 2 —O— or —N—CH 2 —CH 2 —; L is a direct bond or methylene; A 1  and A 2  are C—H, or one of A 1  and A 2  is C—H and the other is N; X 1  is group X R 1  is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 3 -C 6 cycloalkyl; R 2  is chlorodifluoromethyl or trifluoromethyl; each R 3  is independently bromo, chloro, fluoro or trifluoromethyl; R 4  is hydrogen, halogen, methyl, halomethyl or cyano; R 5  is hydrogen; or R 4  and R 5  together form a bridging 1,3-butadiene group; p is 2 or 3. Preferably the methods are for control of stemborer, leaffolder, hoppers, Gall midge, whorl maggot, Rice bugs, and/or Black bugs.

The present invention relates to a method of controlling insects, inparticular insects that infest rice.

Compounds that are insecticidally, acaricidally, nematicidally and/ormoluscicidally active by antagnonism of the gamma-aminobutyric acid(GABA)-gated chloride channel, and which comprise a partially saturatedheterocycle that is substituted by a haloalkyl substituent and one ortwo optionally substituted aromatic or heteroaromatic rings, represent anew class of pesticides that are described for example in Ozoe et al.Biochemical and Biophysical Research Communications, 391 (2010) 744-749.Compounds from this class are broadly described in WO 2005/085216(EP1731512), WO 2007/123853, WO 2007/075459, WO 2009/002809, WO2008/019760, WO 2008/122375, WO 2008/128711, WO 2009/097992, WO2010/072781, WO 2010/072781, WO 2008/126665, WO 2007/125984, WO2008/130651, JP 2008110971, JP 2008133273, JP 2009108046, WO2009/022746, WO 2009/022746, WO 2010/032437, WO 2009/080250, WO2010/020521, WO 2010/025998, WO 2010/020522, WO 2010/084067, WO2010/086225, WO 2010/149506 and WO 2010/108733.

It has now surprisingly been found that particular insecticides fromthis new class of gamma-aminobutyric acid (GABA)-gated chloride channelantagonists (disclosed in e.g. WO2011/067272) are highly effective atcontrolling certain pests in rice.

These compounds therefore represent an important new solution forsafeguarding crops of useful plants, particularly rice crops, frominsects that infest rice crops, particularly where the insects areresistant to current methods.

In a first aspect the invention provides a method comprising applying toa crop of rice plants, the locus thereof, or propagation materialthereof, a compound of formula I

wherein

—B¹—B²—B³— is —C═N—O—, —C═N—CH₂—, —C═CH₂—O— or —N—CH₂—CH₂—;

L is a direct bond or methylene;A¹ and A² are C—H, or one of A¹ and A² is C—H and the other is N;X¹ is group X

R¹ is C₁-C₄alkyl, C₁-C₄haloalkyl or C₃-C₆cycloalkyl;R² is chlorodifluoromethyl or trifluoromethyl;each R³ is independently bromo, chloro, fluoro or trifluoromethyl;R⁴ is hydrogen, halogen, methyl, halomethyl or cyano;R⁵ is hydrogen;or R⁴ and R⁵ together form a bridging 1,3-butadiene group;p is 2 or 3.

The method may be for controlling and/or preventing insects selectedfrom the group consisting of stemborer, leaffolder, hoppers, Gall midge,whorl maggot, Rice bugs, and Black bugs.

In one embodiment the invention provides a method of controlling and/orpreventing stemborer in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing stemborer, particularlyin rice. The stemborer may be resistant to other insecticides. Examplesof stemborers include Chilo sp, Chilo suppressalis, Chilo polychrysus,Chilo auricilius, Scirpophaga spp., Scirpophaga incertulas, Scirpophagainnotata, Scirpophaga nivella Sesamia sp, Sesamia inferens. In a furtheraspect the invention provides a method for obtaining regulatory approvalfor the use of one or more of a compound of formula I to controlstemborer, preferably in rice, comprising at least one step of referringto, submitting or relying on biological data showing that said activeingredient reduces insect pressure.

In one embodiment the invention provides a method of controlling and/orpreventing leaffolder in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing leaffolder, particularlyin rice. The leaffolder may be resistant to other insecticides. Examplesof leaffolders include Cnaphalocrocis spp., Cnaphalocrocis medinalis,Marasmia spp., Marasmia patnalis, Marasmia exigua. In a further aspectthe invention provides a method for obtaining regulatory approval forthe use of one or more of a compound of formula I to control leaffolder,preferably in rice, comprising at least one step of referring to,submitting or relying on biological data showing that said activeingredient reduces insect pressure.

In one embodiment the invention provides a method of controlling and/orpreventing hoppers in rice comprising applying to a crop of rice plants,the locus thereof, or propagation material thereof, a compound offormula I. In one embodiment the invention provides use of a compound offormula I for controlling and/or preventing hoppers, particularly inrice. The hoppers may be resistant to other insecticides. Examples ofHoppers include Nephotettix spp., Nephotettix virescens, Nephotettixnigropictus, Nephotettix malayanus, Nephotettix cincticeps, Nilaparvatalugens, Sogatella furcifera. In a further aspect the invention providesa method for obtaining regulatory approval for the use of one or more ofa compound of formula I to control hoppers, preferably in rice,comprising at least one step of referring to, submitting or relying onbiological data showing that said active ingredient reduces insectpressure.

In one embodiment the invention provides a method of controlling and/orpreventing Gall midge in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing Gall midge, particularlyin rice. The Gall midge may be resistant to other insecticides. Examplesof Gall midge include Orseolia sp, Orseolia oryzae. In a further aspectthe invention provides a method for obtaining regulatory approval forthe use of one or more of a compound of formula I to control Gall midge,preferably in rice, comprising at least one step of referring to,submitting or relying on biological data showing that said activeingredient reduces insect pressure.

In one embodiment the invention provides a method of controlling and/orpreventing whorl maggot in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing whorl maggot,particularly in rice. The whorl maggot may be resistant to otherinsecticides. Examples of whorl maggots include Hydrellia sp, Hydrelliaphilippina. In a further aspect the invention provides a method forobtaining regulatory approval for the use of one or more of a compoundof formula I to control whorl maggots, preferably in rice, comprising atleast one step of referring to, submitting or relying on biological datashowing that said active ingredient reduces insect pressure.

In one embodiment the invention provides a method of controlling and/orpreventing Rice bugs in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing Rice bugs, particularlyin rice. The Rice bugs may be resistant to other insecticides. Examplesof rice bugs include Leptocorisa sp, Leptocorisa oratorius, Leptocorisachinensis, Leptocorisa acuta. In a further aspect the invention providesa method for obtaining regulatory approval for the use of one or more ofa compound of formula I to control Rice bugs, preferably in rice,comprising at least one step of referring to, submitting or relying onbiological data showing that said active ingredient reduces insectpressure.

In one embodiment the invention provides a method of controlling and/orpreventing Black bugs in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I. In one embodiment the invention provides use of a compoundof formula I for controlling and/or preventing Black bugs, particularlyin rice. The Black bugs may be resistant to other insecticides. Examplesof Black bugs include Scotinophara sp, Scotinophara coarctata,Scotinophara lurida, Scotinophara latiuscula. In a further aspect theinvention provides a method for obtaining regulatory approval for theuse of one or more of a compound of formula I to control Black bugs,preferably in rice, comprising at least one step of referring to,submitting or relying on biological data showing that said activeingredient reduces insect pressure.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds. The invention also covers salts andN-oxides of the compounds of the invention.

Preferred substituent definitions are described below and may becombined in any combination, including with original definitions.

—B¹—B²—B³— is preferably —C═N—O—.

A¹ and A² are preferably C—H.

Preferably X¹ is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-,3-fluoro-4-chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-,3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-,3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-,3-chloro-5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-,3,4-dichloro-5-(trifluoromethyl)phenyl-,3,5-bis(trifluoromethyl)phenyl-,4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-,more preferably 3-chloro-5-bromophenyl-,3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-,3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-,3-(trifluoromethyl)phenyl-, 3,5-dichloro-4-bromophenyl-,3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or3,4-dichlorophenyl-, even more preferably 3,5-dichloro-phenyl,3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-,3,5-bis(trifluoromethyl)phenyl, most preferably R⁴ is3,5-dichloro-phenyl.

R¹ is preferably methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl,trifluoroethyl, difluoroethyl. Ethyl and trifluoroethyl are particularlypreferred.

R² is preferably trifluoromethyl.

Preferably each R³ is independently chlorine or fluorine, mostpreferably chlorine.

R⁴ is preferably chloro or methyl, most preferably methyl.

R⁵ is preferably hydrogen.

L is preferably a direct bond.

In one group of compounds —B¹—B²—B³— is —C═N—O—.

In one group of compounds —B¹—B²—B³— is —C═N—CH₂—.

In one group of compounds —B¹—B²—B³— is —C═CH₂—O—.

In one group of compounds —B¹—B²—B³— is —N—CH₂—CH₂—.

In one embodiment A¹ and A² are C—H; R² is trifluoromethyl, and R⁵ ishydrogen.

In one embodiment A¹ and A² are C—H, R² is trifluoromethyl, R⁵ ishydrogen and L is a direct bond.

In one embodiment —B¹—B²—B³— is —C═N—O—, A¹ and A² are C—H, R² istrifluoromethyl, R⁵ is hydrogen and L is a direct bond.

In one embodiment —B¹—B²—B³— is —C═N—O—, A¹ and A² are C—H, R² istrifluoromethyl, R⁴ is halogen or methyl, R⁵ is hydrogen and L is adirect bond.

In a preferred embodiment —B¹—B²—B³— is —C═N—O—, A¹ and A² are C—H, R²is trifluoromethyl, R³ is chloro or fluoro, R⁴ is halogen or methyl, R⁵is hydrogen and L is a direct bond.

In a very preferred embodiment —B¹—B²—B³— is —C═N—O—., A¹ and A² areC—H, R² is trifluoromethyl, R³ is chloro or fluoro, R⁴ is halogen ormethyl, R⁵ is hydrogen and L is a direct bond, and the method is amethod of controlling and/or preventing infestation of hoppers,preferably brown plant hopper (Nilaparvata lugens) or stemborer (inparticular Chilo sp,) in a crop of useful plants, preferably rice, verypreferably wherein the method is a method of controlling and/orpreventing infestation of hoppers, preferably brown plant hopper(Nilaparvata lugens) in a crop of useful plants, preferably rice.

In one embodiment A¹ and A² are C—H, R² is trifluoromethyl, R⁴ ismethyl, R⁵ is hydrogen, each R³ is chlorine, p is 2.

In one embodiment R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g.methyl or ethyl, e.g. ethyl.

In one embodiment X¹ is group Xa

In one embodiment R¹ is C₁-C₅alkyl, e.g. methyl, ethyl or propyl, e.g.methyl or ethyl, e.g. ethyl and X¹ is group Xa.

In one embodiment R¹ is methyl.

In one embodiment R¹ is ethyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl.

In one embodiment R¹ is 2,2-difluoroethyl.

In one embodiment X¹ is 3,5-dichlorophenyl.

In one embodiment X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,5-dichlorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,4,5-trichlorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is3,4,5-trichlorophenyl.

In all embodiments of the invention the method is preferably a method ofcontrolling and/or preventing infestation of hoppers, preferably brownplant hopper (Nilaparvata lugens) or stemborer (in particular Chilo sp,)in a crop of useful plants, preferably rice. Method of controllingand/or preventing infestation of hoppers, preferably brown plant hopper(Nilaparvata lugens) in a crop of useful plants, preferably rice is mostpreferred.

Compounds of formula I may exist as compounds of formula I* or compoundsof formula I**.

Compounds of formula I** are more biologically active than compounds offormula I*. Compounds of formula I may be a mixture of compounds I* andI** in any ratio e.g. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to1:10, e.g. a substantially 50:50 molar ratio. Preferably the compound offormula I is a racemic mixture of the compounds of formula I** and I* oris enantiomerically enriched for the compound of formula I**. Forexample, when the compound of formula I is an enantiomerically enrichedmixture of formula I**, the molar proportion of compound I** compared tothe total amount of both enantiomers is for example greater than 50%,e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or atleast 99%. In one embodiment the compound of formula I is a compound offormula I** in substantially pure form, e.g. it is providedsubstantially in the absence of the alternative enantiomer.

Compounds of formula I may also exist as compounds of formula I′ orcompounds of formula I″.

(S=S stereochemistry, R=R stereochemistry)

Compounds of formula I″ are often more biologically active thancompounds of formula I′. The compound of formula I may be a mixture ofcompounds I′ and I″ in any ratio e.g. in a molar ratio of 1:99 to 99:1,e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. Preferablythe compound of formula I is a racemic mixture of the compounds offormula I″ and I′ or is enantiomerically enriched for the compound offormula I″. For example, when the compound of formula I is anenantiomerically enriched mixture of formula I″, the molar proportion ofcompound I″ compared to the total amount of both enantiomers is forexample greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90,95, 96, 97, 98, or at least 99%. In a preferred embodiment the compoundof formula I is a compound of formula I″ in substantially pure form,e.g. it is provided substantially in the absence of the alternativeenantiomer.

The above stereocentres give rise to four stereoisomers:

In one embodiment the compound of formula I is a mixture comprisingcompounds I-i, and I-iv, wherein the mixture is enriched for thecompound of formula I-iv, e.g. the molar proportion of compound I-ivcompared to the total amount of the four isomers is for example greaterthan 25%, e.g. at least 30, 35, 40, 50 55, 60, 65, 70, 75, 80, 85, 90,95, 96, 97, 98, or at least 99%.

In another embodiment the compound of formula I is a mixture comprisingcompounds I-i, I-ii, I-iii and I-iv, wherein the molar amount of thecompound of formuila I-iv is greater than the molar amount of thecompound of formula I-i, and the molar amount of the compound I-ii, andthe molar amount of the compound of formula I-iii, in other words, thecompound of formula I-iv is the most abundant isomer in the mixture. Forexample the molar amount of compound of formula I-iv is at least 1, 2,5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 56, 70, 75, 80, 85, 90,or even at least 95% greater than the combined amount of the compound offormula I-iv and I-i, the combined amount of the compound of formulaI-iv and I-ii, and the combined amount of the compound of formula I-ivand I-iii.

Although B¹—B²—B³ is shown above as C═N—O, the same applies in respectof the stereoisomers when B¹—B²—B³ is —C═N—CH₂—, —C═CH₂—O— and—N—CH₂—CH₂—.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g. methylor ethyl, e.g. ethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g. methylor ethyl, e.g. ethyl and X¹ is group Xa.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is methyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is ethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is 2,2,2-trifluoroethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is 2,2-difluoroethyl.

Preferred compounds of formula I are shown in the Tables below.

TABLE A Compounds of formula (I-a)

(I-a)Table A provides 78 compounds and mixtures of formula (I-a) wherein R¹has the values listed in table X below. The symbols * and ** indicatethe location of the chiral centres.

TABLE B Compounds of formula (I-b)

(I-b)Table B provides 78 compounds and mixtures of formula (I-b) wherein R¹has the values listed in table X below. The symbols * and ** indicatethe location of the chiral centres.

TABLE C Compounds of formula (I-c)

(I-c)Table C provides 78 compounds and mixtures of formula (I-c) wherein R¹has the values listed in table X below. The symbols * and ** indicatethe location of the chiral centres.

TABLE D Compounds of formula (I-d)

(I-d)Table D provides 78 compounds and mixtures of formula (I-d) wherein R¹has the values listed in table X below. The symbols * and ** indicatethe location of the chiral centres.

TABLE E Compounds of formula (I-e)

(I-e)Table E provides 78 compounds and mixtures of formula (I-e) wherein R¹has the values listed in table X below. The symbols * and ** indicatethe location of the chiral centres.

TABLE F Compounds of formula (I-f)

(I-f)Table F provides 78 compounds and mixtures of formula (M) wherein R¹ hasthe values listed in table X below. The symbols * and ** indicate thelocation of the chiral centres.Table X represents Table A when X is A, Table B when X is B, Table Cwhen X is C, Table D when X is D, Table E when X is E, Table F when X isF.

Com- Stereochemistry Stereochemistry pound at at numbers * ** R¹ X.1Racemic mixture Racemic mixture ethyl- X.2 Racemic mixture Racemicmixture butyl- X.3 Racemic mixture Racemic mixture but-2-yl- X.4 Racemicmixture Racemic mixture 3-bromo-propyl- X.5 Racemic mixture Racemicmixture 2,2,2-trifluoro-ethyl- X.6 Racemic mixture Racemic mixture3,3,3-trifluoro-propyl- X.7 Racemic mixture Racemic mixture cyclobutyl-X.8 Racemic mixture Racemic mixture methyl X.9 Racemic mixture Racemicmixture propyl X.10 Racemic mixture Racemic mixture 2,2-difluoro-ethyl-X.11 Racemic mixture Racemic mixture 2-fluoro-ethyl- X.12 S Racemicmixture ethyl- X.13 S Racemic mixture butyl- X.14 S Racemic mixturebut-2-yl- X.15 S Racemic mixture 3-bromo-propyl- X.16 S Racemic mixture2,2,2-trifluoro-ethyl- X.17 S Racemic mixture 3,3,3-trifluoro-propyl-X.18 S Racemic mixture cyclobutyl- X.19 S Racemic mixture methyl X.20 SRacemic mixture propyl X.21 S Racemic mixture 2,2-difluoro-ethyl- X.22 SRacemic mixture 2-fluoro-ethyl- X.23 Racemic mixture Racemic mixtureisopropyl X.24 Racemic mixture Racemic mixture cyclopropyl X.25 SRacemic mixture isopropyl X.26 S Racemic mixture cyclopropyl X.27Racemic mixture S ethyl- X.28 Racemic mixture S butyl- X.29 Racemicmixture S but-2-yl- X.30 Racemic mixture S 3-bromo-propyl- X.31 Racemicmixture S 2,2,2-trifluoro-ethyl- X.32 Racemic mixture S3,3,3-trifluoro-propyl- X.33 Racemic mixture S cyclobutyl- X.34 Racemicmixture S methyl X.35 Racemic mixture S propyl X.36 Racemic mixture S2,2-difluoro-ethyl- X.37 Racemic mixture S 2-fluoro-ethyl- X.38 S Sethyl- X.39 S S butyl- X.40 S S but-2-yl- X.41 S S 3-bromo-propyl- X.42S S 2,2,2-trifluoro-ethyl- X.43 S S 3,3,3-trifluoro-propyl- X.44 S Scyclobutyl- X.45 S S methyl X.46 S S propyl X.47 S S 2,2-difluoro-ethyl-X.48 S S 2-fluoro-ethyl- X.49 Racemic mixture S isopropyl X.50 Racemicmixture S cyclopropyl X.51 S S isopropyl X.52 S S cyclopropyl X.53Racemic mixture R ethyl- X.54 Racemic mixture R butyl- X.55 Racemicmixture R but-2-yl- X.56 Racemic mixture R 3-bromo-propyl- X.57 Racemicmixture R 2,2,2-trifluoro-ethyl- X.58 Racemic mixture R3,3,3-trifluoro-propyl- X.59 Racemic mixture R cyclobutyl- X.60 Racemicmixture R methyl X.61 Racemic mixture R propyl X.62 Racemic mixture R2,2-difluoro-ethyl- X.63 Racemic mixture R 2-fluoro-ethyl- X.64 S Rethyl- X.65 S R butyl- X.66 S R but-2-yl- X.67 S R 3-bromo-propyl- X.68S R 2,2,2-trifluoro-ethyl- X.69 S R 3,3,3-trifluoro-propyl- X.70 S Rcyclobutyl- X.71 S R methyl X.72 S R propyl X.73 S R 2,2-difluoro-ethyl-X.74 S R 2-fluoro-ethyl- X.75 Racemic mixture R isopropyl X.76 Racemicmixture R cyclopropyl X.77 S R isopropyl X.78 S R cyclopropyl

The compounds of the invention may be made by a variety of methods asshown in Schemes 1 to 3.

1) Compounds of formula (I), can be prepared by reacting a compound offormula (II) wherein R is OH, C₁-C₆alkoxy or Cl, F or Br, with an amineof formula (III) as shown in Scheme 1. When R is OH such reactions areusually carried out in the presence of a coupling reagent, such asN,N′-dicyclohexyl-carbodiimide (“DCC”),1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) orbis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-Cl”), in the presenceof a base, and optionally in the presence of a nucleophilic catalyst,such as hydroxybenzotriazole (“HOBT”). When R is Cl, such reactions areusually carried out in the presence of a base, and optionally in thepresence of a nucleophilic catalyst. Alternatively, it is possible toconduct the reaction in a biphasic system comprising an organic solvent,preferably ethyl acetate, and an aqueous solvent, preferably a solutionof sodium hydrogen carbonate. When R is C₁-C₆alkoxy it is sometimespossible to convert the ester directly to the amide by heating the esterand amine together in a thermal process. Suitable bases includepyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) ordiisopropylethylamine (Hunig's base). Preferred solvents areN,N-dimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane,ethyl acetate and toluene. The reaction is carried out at a temperatureof from 0° C. to 100° C., preferably from 15° C. to 30° C., inparticular at ambient temperature Amines of formula (III) are eitherknown in the literature or can be prepared using methods known to aperson skilled in the art.

2) Acid halides of formula (II), wherein R is Cl, F or Br, may be madefrom carboxylic acids of formula (II), wherein R is OH, under standardconditions, as described for example in WO2009/080250.

3) Carboxylic acids of formula (II), wherein R is OH, may be formed fromesters of formula (II), wherein R is C₁-C₆alkoxy as described forexample in WO 2009/080250.

4) Compounds of formula (I) can be prepared by reacting a compound offormula (IV) wherein X^(B) is a leaving group, for example a halogen,such as bromo, with carbon monoxide and an amine of formula (III), inthe presence of a catalyst, such as palladium(II) acetate orbis-(triphenylphosphine)palladium(II) dichloride, optionally in thepresence of a ligand, such as triphenylphosphine, and a base, such assodium carbonate, pyridine, triethylamine, 4-(dimethylamino)-pyridine(“DMAP”) or diisopropylethylamine (Hunig's base), in a solvent, such aswater, N,N-dimethylformamide or tetrahydrofuran. The reaction is carriedout at a temperature of from 50° C. to 200° C., preferably from 100° C.to 150° C. The reaction is carried out at a pressure of from 50 to 200bar, preferably from 100 to 150 bar.

5) Compounds of formula (IV) wherein X^(B) is a leaving group, forexample a halogen, such as bromo, can be made by a various of methods,for example as described in WO 2009/080250.

6) Alternatively, compounds of formula (I), can be prepared by variousmethods from an intermediate of formula (V) as shown in Scheme 2 whereinX^(B) is a leaving group, for example a halogen, such as bromo, or X^(B)is cyano, formyl or acetyl according to similar methods to thosedescribed in WO09/080250. An intermediate of formula (V) can be preparedfor example from an intermediate of formula (VI) as described in thesame reference.

7) Alternatively, compounds of formula (I) can be prepared by variousmethods from an intermediate of formula (VII) as shown in Scheme 3wherein X^(C) is X^(C)-1 or X^(C)-2

according to similar methods to those described in WO 2009/080250.

8) Compounds of formula (VII) wherein X^(C) is X^(C) is X^(C)-1 orX^(C)-2 can be prepared from a compound of formula (Va) from a compoundof formula (VII) wherein X^(C) is CH₂-halogen using similar methods tothose described in WO 2009/080250.

9) Compounds of formula (VII) wherein X^(C) is CH₂-halogen, such asbromo or chloro, can be prepared by reacting a methyl ketone of formula(Va) with a halogenating agent, such as bromine or chlorine, in asolvent, such as acetic acid, at a temperature of from 0° C. to 50° C.,preferably from ambient temperature to 40° C.

Other methods for the preparation of compounds of formula I aredescribed in PCT/EP2010/068605, which is incorporated herein byreference.

In one embodiment the invention provides a compound selected from TablesA to F for use against rice pests.

In one embodiment the invention provides a compound selected from TablesA to F for use against stemborer, particularly in rice.

Examples of stemborers include Chilo sp, Chilo suppressalis, Chilopolychrysus, Chilo auricilius, Scirpophaga spp., Scirpophaga incertulas,Scirpophaga innotata, Scirpophaga nivella Sesamia sp, Sesamia inferens.

In one embodiment the invention provides a compound selected from TablesA to F for use against leaffolder, particularly in rice.

Examples of leaffolders include Cnaphalocrocis spp., Cnaphalocrocismedinalis, Marasmia spp., Marasmia patnalis, Marasmia exigua.

In one embodiment the invention provides a compound selected from TablesA to F for use against hoppers, particularly in rice.

Examples of Hoppers include Nephotettix spp., Nephotettix virescens,Nephotettix nigropictus, Nephotettix malayanus, Nephotettix cincticeps,Nilaparvata lugens, Sogatella furcifera.

In one embodiment the invention provides a compound selected from TablesA to F for use against gallmidge, particularly in rice.

Examples of Gall midge include Orseolia sp, Orseolia oryzae.

In one embodiment the invention provides a compound selected from TablesA to F for use against whorl maggot, particularly in rice.

Examples of whorl maggots include Hydrellia sp, Hydrellia philippina.

In one embodiment the invention provides a compound selected from TablesA to F for use against Rice bugs, particularly in rice.

Examples of rice bugs include Leptocorisa sp, Leptocorisa oratorius,Leptocorisa chinensis, Leptocorisa acuta.

In one embodiment the invention provides a compound selected from TablesA to F for use against Black bugs, particularly in rice.

Examples of Black bugs include Scotinophara sp, Scotinophara coarctata,Scotinophara lurida, Scotinophara latiuscula.

Use of the compounds of the invention against Brown plant hopper(Nilaparvata lugens) and/or stemborer (in particular Chilo sp,) isparticularly preferred. Use of the compounds of the invention againstBrown plant hopper (Nilaparvata lugens) is most preferred.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of a plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Application may be before infestation or when the pest is present.Application of the compounds of the invention can be performed accordingto any of the usual modes of application, e.g. foliar, drench, soil, infurrow etc. However, control of Anthonomus grandis s is usually achievedby foliar application, which is the preferred mode of applicationaccording to the invention.

Application of the compounds of the invention is preferably to a crop ofcotton plants, the locus thereof or propagation material thereof.

The compounds of the invention may be applied to plant parts. Plantparts are to be understood as meaning all parts and organs of plantsabove and below the ground, such as shoot, leaf, flower and root,examples which may be mentioned being leaves, needles, stalks, stems,flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. Theplant parts also include harvested material, and vegetative andgenerative propagation material, for example cuttings, tubers, rhizomes,offshoots and seeds. Treatment according to the invention of the plantsand plant parts with the active compounds can be carried out directly orby allowing the compounds to act on their surroundings, habitat orstorage space by the customary treatment methods, for example byimmersion, spraying, evaporation, fogging, scattering, painting on,injecting and, in the case of propagation material, in particular in thecase of seed, also by applying one or more coats.

The compounds of the invention are suitable for use on any plant(preferably cotton plant), including those that have been geneticallymodified to be resistant to active ingredients such as herbicides, or toproduce biologically active compounds that control infestation by plantpests.

The term “plant” as used herein includes seedlings, bushes and trees.Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides or classes of herbicides (e.g. ALS-,GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods ofbreeding or by genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding is Clearfield® summer rape (canola). Examples ofcrops that have been rendered tolerant to herbicides by geneticengineering methods include e.g. glyphosate- and glufosinate-resistantmaize varieties commercially available under the trade namesRoundupReady® and LibertyLink®.

Compounds of formula I may be used on transgenic plants (includingcultivars) obtained by genetic engineering methods and/or byconventional methods. These are understood as meaning plants havingnovel properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. Depending onthe plant species or plant cultivars, their location and growthconditions (soils, climate, vegetation period, diet), the treatmentaccording to the invention may also result in superadditive“synergistic”) effects.

Thus, for example, reduced application rates and/or a widening of theactivity spectrum and/or an increase in the activity of the substancesand compositions which can be used according to the invention, betterplant growth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, higher quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products are possible, which exceed the effects which wereactually to be expected.

The preferred transgenic plants or plant cultivars which are to betreated according to the invention include all plants which, by virtueof the genetic modification, received genetic material which impartsparticularly advantageous, useful traits to these plants. Examples ofsuch traits are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, higher quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products.

Further and particularly emphasized examples of such traits are a betterdefence of the plants against animal and microbial pests, such asagainst insects, mites, phytopathogenic fungi, bacteria and/or viruses,and also increased tolerance of the plants to certain herbicidallyactive compounds.

Examples of transgenic plants which may be mentioned are the importantcrop plants, such as cereals (wheat, rice), maize, soybean, potatoes,sugar beet, tomatoes, peas and other vegetable varieties, cotton,tobacco, oilseed rape and also fruit plants (with the fruits apples,pears, citrus fruits and grapes). Transgenic cotton is of particularinterest.

Compounds of formula I may be used on transgenic plants that are capableof producing one or more pesticidal proteins which confer upon thetransgenic plant tolerance or resistance to harmful pests, e.g. insectpests, nematode pests and the like. Such pesticidal proteins include,without limitation, Cry proteins from Bacillus thuringiensis Cry1Ab,Cry1Ac, Cry1F, Cry2Ab, Cry2Ae, Cry3A, Cry3Bb, or Cry9C; engineeredproteins such as modified Cry3A (U.S. Pat. No. 7,030,295) or Cry1A.105;or vegetative insecticidal proteins such as Vip1, Vip2 or Vip3. A fulllist of Bt Cry proteins and VIPs useful in the invention can be found onthe worldwide web at Bacillus thuringiensis Toxin Nomenclature Databasemaintained by the University of Sussex (see also, Crickmore et al.(1998) Microbiol. Mol. Biol. Rev. 62:807-813). Other pesticidal proteinsuseful in the invention include proteins of bacteria colonizingnematodes, e.g. Photorhabdus spp. or Xenorhabdus spp.; toxins producedby animals, such as scorpion toxins, arachnid toxins, wasp toxins, orother insect-specific neurotoxins; toxins produced by fungi, suchStreptomycetes toxins, plant lectins, such as pea or barley lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. Further examples of such pesticidal proteins or transgenicplants capable of synthesizing such proteins are disclosed, e.g., inEP-A 374753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451878, WO03/18810 and WO 03/52073. The methods for producing such transgenicplants are generally known to the person skilled in the art and some ofwhich are commercially available such as Agrisure®CB (P1) (cornproducing Cry1Ab), Agrisure®RW (P2) (corn producing mCry3A), Agrisure®Viptera (P3) (corn hybrids producing Vip3Aa); Agrisure300GT (P4) (cornhybrids producing Cry1Ab and mCry3A); YieldGard® (P5) (corn hybridsproducing the Cry1Ab protein), YieldGard® Plus (P6) (corn hybridsproducing Cry1Ab and Cry3Bb1), Genuity® SmartStax® (P7) (corn hybridswith Cry1A.105, Cry2Ab2, Cry1F, Cry34/35, Cry3Bb); Herculex® I (P8)(corn hybrids producing Cry1Fa) and Herculex®RW (P9) (corn hybridsproducing Cry34Ab1, Cry35Ab1 and the enzymePhosphinothricin-N-Acetyltransferase [PAT]); NuCOTN®33B (P10) (cottoncultivars producing Cry1Ac), Bollgard®I (P11) (cotton cultivarsproducing Cry1Ac), Bollgard®II (P12) (cotton cultivars producing Cry1Acand Cry2Ab2) and VIPCOT® (P13) (cotton cultivars producing a Vip3Aa).Soybean Cyst Nematode resistance soybean (SCN®—Syngenta (P14)) andsoybean with Aphid resistant trait (AMT® (P15)) are also of interest.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10 (P16).Genetically modified Zea mays which has been rendered resistant toattack by the European corn borer (Ostrinia nubilalis and Sesamianonagrioides) by transgenic expression of a truncated CryIA(b) toxin.Bt11 maize also transgenically expresses the enzyme PAT to achievetolerance to the herbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10 (P17).Genetically modified Zea mays which has been rendered resistant toattack by the European corn borer (Ostrinia nubilalis and Sesamianonagrioides) by transgenic expression of a CryIA(b) toxin. Bt176 maizealso transgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l′Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10 (P18). Maizewhich has been rendered insect-resistant by transgenic expression of amodified CryIIIA toxin. This toxin is Cry3A055 modified by insertion ofa cathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9 (P19). MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02. (P20)

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. (P21)Genetically modified maize for the expression of the protein Cry1F forachieving resistance to certain Lepidoptera insects and of the PATprotein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Further examples of transgenic plants, and of very high interest, arethose carrying traits conferring resistance to 2.4 D (e.g. Enlist®)(e.g. WO 2011066384) (, glyphosate (e.g. Roundup Ready® (P24), RoundupReady 2 Yield® (P25)), sulfonylurea (e.g. STS®) (P26), glufosinate (e.g.Liberty Link® (P27), Ignite® (P28)), Dicamba (P29) (Monsanto), HPPDtolerance (P30) (e.g. isoxaflutole herbicide) (Bayer CropScience,Syngenta). Double or triple stacks of any of the traits described hereare also of interest, including glyphosate and sulfonyl-urea tolerance((e.g. Optimum GAT®) (P31), plants stacked with STS® and Roundup Ready®(P32) or plants stacked with STS® and Roundup Ready 2 Yield® (P33)),dicamba and glyphosate tolerance (P34) (Monsanto). Of particularinterest are soybean plants carrying trains conferring resistance to 2.4D (e.g. Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. Liberty Link®,Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g. isoxaflutoleherbicide) (Bayer CropScience, Syngenta).

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

Further examples of transgenic plants, and of very high interest, arethose carrying traits conferring resistance to 2.4 D (e.g. Enlist®)(e.g. WO 2011066384) (, glyphosate (e.g. Roundup Ready® (P24), RoundupReady 2 Yield® (P25)), sulfonylurea (e.g. STS®) (P26), glufosinate (e.g.Liberty Link® (P27), Ignite® (P28)), Dicamba (P29) (Monsanto), HPPDtolerance (P30) (e.g. isoxaflutole herbicide) (Bayer CropScience,Syngenta). Double or triple stacks of any of the traits described hereare also of interest, including glyphosate and sulfonyl-urea tolerance((e.g. Optimum GAT®) (P31), plants stacked with STS® and Roundup Ready®(P32) or plants stacked with STS® and Roundup Ready 2 Yield® (P33)),dicamba and glyphosate tolerance (P34) (Monsanto). Of particularinterest are soybean plants carrying trains conferring resistance to 2.4D (e.g. Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. Liberty Link®,Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g. isoxaflutoleherbicide) (Bayer CropScience, Syngenta).

Examples of cotton transgenic events include MON 531/757/1076 (BollgardI®-Monsanto), MON1445 (Roundup ready Cotton®-Monsanto), MON531 x MON1445(Bollgard I+RR®—Monsanto), MON15985 (Genuity Bollgard IICotton®-Monsanto), MON88913 (Genuity RR FLEX Cotton®-Monsanto), MON15985x MON1445 (Genuity Bollgard II+RR FELX Cotton®-Monsanto), MON15983 xMON88913 (Genuity Bollgard II+RR FLEX Cotton®-Monsanto), MON15985(FibreMax Bollgard II Cotton®-Monsanto), LL25 (FibreMax LL Cotton®-BCSStoneville), GHB614 (FibreMax GlyTol Cotton®-BCS Stoneville), LL25 xMON15985 (FibreMax LL Bollgard II Cotton®—BCS Stoneville/Monsanto),GHB614 x LL25 (FibreMax LL GlyTol Cotton®-BCS Stoneville), GHB614 x LL25x MON15985 (FibreMax RR GlyTol Bollgard II Cotton®-BCS Stoneville),MON88913 x MON15985 (FibreMax LL GlyTol Bollgard II Cotton®-Monsanto),MON88913 (FibreMax RR Flex Cotton®-Monsanto), GHB119+T304-40(Twinlink®-BCS Stoneville), GHB119+T304-40 x LL25 x GHB614 (Twinlink LLGT®-BCS Stoneville), 3006-210-23×281-24-236 (PhytoGen Widestrike InsectProtection®-Dow), 3006-210-23×281-24-236 x MON88913 (PhytoGen WidestrikeInsect Protection+RR FLEX-® Dow/Monsanto), 3006-210-23×281-24-236 xMON1445 ((PhytoGen Widestrike Insect Protection+RR®-Dow/Monsanto),MON1445 (PhytoGen Roundup Ready®-Monsanto), MON88913 (PhytoGen RoundupReady FLEX®-Monsanto), COT102 x COT67B (Vipcot®-Syngenta), COT102 xCOT67B x MON88913 (Vipcot RR FLEX®-Syngenta/Monsanto), 281-24-236 (Dow),3006-210-23 (Dow), COT102 (Syngenta), COT67B (Syngenta), T304-40 (BCSStoneville).

Examples of Soy transgenic events include MON87701 x MON89788 (GenuityRoundup ready 2 Yield Soybeans®-Monsanto), MON89788 (RoundupReady2Yield®, RR2Y®-Monsanto), MON87708 (Monsanto), 40-3-2 (RoundupReady®, RR1®-Monsanto), MON87701 (Monsanto), DAS-68416 (Enlist WeedControl System®-Dow), DP356043 (Optimum GAT®-Pioneer), A5547-127(LibertyLink Soybean®-Bayercropscience), A2704-12 (Bayercropscience),GU262 (Bayercropscience), W62 W98 (Bayercropscience), CRV127(Cultivance®-BASF/EMBRAPA) SYHT0H2 (WO2012/082548).

Examples of Maize transgenic events include T25 (LibertyLink®,LL®-Bayerscropscience), DHT-1 (Dow), TC1507 (Herculex I®-Dow),DAS59122-7 (Herculex RW®-Dow), TC1507+DAS59122-7-Herculex Xtra®-Dow),TC1507 x DAS-59122-7 x NK603 (Herculex Xtra+RR®—Dow), TC1507 x DAS-59122x MON88017 x MON89034 (Genuity Smartstax Corn®, Genuity Smartstax RIBComplete®-Monsanto/Dow), MON89034 x NK603 (Genuity VT doublePRO®—Monsanto), MON89034+MON88017 (Genuity VT Triple PRO®-Monsanto),NK603 (Roundup Ready 2®, RR2®-Monsanto), MON810 (YieldGard BT®,Yieldgard Cornborer®-Monsanto), MON810 x NK603 (YieldGard cornborer RRCorn 2®-Monasnto), MON810 x MON863 (YieldGard Plus®—Monsanto), MON863 xMON810 x NK603 (YieldGard Plus+RR Corn2®/YieldGard RR Maize®—Monsanto),MON863 x NK603 (YieldGard Rotworm+RR Corn 2®-Monsanto), MON863(YieldBard RW®-Monsanto), MON89034 (YieldGard RW®-Monsanto), MON88017(YieldGard VT RW®—Monsanto), MON810+MON88017 (YieldGard VTTriple®-Monsanto), MON88017+MON89034 (YieldGard VT TriplePro®-Monsanto), Bt11+MIR604+GA21 (Agrisure 3000®-Syngenta),Bt11+TC1507+MIR604+5307+GA21 (Syngenta),Bt11+TC1507+MIR604+DAS59122+GA21 (Agrisure 3122®-Syngenta), BT11(Agrisure CB®-Syngenta), GA21-(Agrisure GT®-Syngenta), MIR604 (AgrisureRW®-Syngenta), Bt11+MIR162 (Agrisure TL VIP®-Syngenta), BT11+MIR162+GA21(Agrisure Viptra 31100-Syngenta), BT11+MIR162+MIR604 (Agrisure™3100®—Syngenta), Event3272+BT11+MIR604+GA21 (Syngenta),BT11+MIR1692+MIR604+GA21 (Agrisure Viptera 3111®-Syngenta),BT11+MIR162+TC1507+GA21 (Agrisure Viptera 3220®—Syngenta),BT11+MIR162+TC1507+MIR604+5307+GA21 (Agrisure Viptera 3222®-Syngenta),MIR162 (Syngenta), BT11+GA21+MIR162+MIR604+5307 (Syngenta), 5307(Syngenta).

Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield®) (for example maize).

These statements also apply to plant cultivars having these genetictraits or genetic traits still to be developed, which plant cultivarswill be developed and/or marketed in the future.

The compounds of the invention are suitable for use on any cotton plant,including those that have been genetically modified to be resistant toactive ingredients such as herbicides, or to produce biologically activecompounds that control infestation by plant pests, e.g. BT cotton.

A compound of the invention may be used in mixtures with fertilizers(for example nitrogen-, potassium- or phosphorus-containingfertilizers). Suitable formulation types include granules of fertilizer.The mixtures preferably contain up to 25% by weight of the compound ofthe invention.

The invention therefore also provides a fertilizer compositioncomprising a fertilizer and a compound of the invention.

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula (I) may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide, e.g. a insecticide, fungicide orherbicide, or a synergist or plant growth regulator where appropriate.An additional active ingredient may provide a composition having abroader spectrum of activity or increased persistence at a locus;synergize the activity or complement the activity (for example byincreasing the speed of effect or overcoming repellency) of the compoundof formula (I); or help to overcome or prevent the development ofresistance to individual components. The particular additional activeingredient will depend upon the intended utility of the composition.Examples of suitable pesticides include the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,esfenvalerate, deltamethrin, cyhalothrin (in particularlambda-cyhalothrin and gamma cyhalothrin), bifenthrin, fenpropathrin,cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox),natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin,prallethrin, acrinathirin, etofenprox or5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate;b) Organophosphates, such as profenofos, sulprofos, acephate, methylparathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon,fenamiphos, monocrotophos, profenofos, triazophos, methamidophos,dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos,fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;c) Carbamates (including aryl carbamates), such as pirimicarb,triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,methomyl or oxamyl;d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,flufenoxuron, diafenthiuron, lufeneron, novaluron, noviflumuron orchlorfluazuron;e) Organic tin compounds, such as cyhexatin, fenbutatin oxide orazocyclotin;f) Pyrazoles, such as tebufenpyrad, tolfenpyrad, ethiprole, pyriprole,fipronil, and fenpyroximate;g) Macrolides, such as avermectins or milbemycins, for exampleabamectin, emamectin benzoate, ivermectin, milbemycin, spinosad,azadirachtin, milbemectin, lepimectin or spinetoram;h) Hormones or pheromones;i) Organochlorine compounds, such as endosulfan (in particularalpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin;j) Amidines, such as chlordimeform or amitraz;k) Fumigant agents, such as chloropicrin, dichloropropane, methylbromide or metam;l) Neonicotinoid compounds, such as imidacloprid, thiacloprid,acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, ornithiazine;m) Diacylhydrazines, such as tebufenozide, chromafenozide ormethoxyfenozide;n) Diphenyl ethers, such as diofenolan or pyriproxifen;o) Ureas such as Indoxacarb or metaflumizone;p) Ketoenols, such as Spirotetramat, spirodiclofen or spiromesifen;q) Diamides, such as flubendiamide, chlorantraniliprole (Rynaxypyr®) orcyantraniliprole;r) Essential oils such as Bugoil®—(PlantImpact); ors) a comopund selected from buprofezine, flonicamid, acequinocyl,bifenazate, cyenopyrafen, cyflumetofen, etoxazole, flometoquin,fluacrypyrim, fluensulfone, flufenerim, flupyradifuone, harpin,iodomethane, dodecadienol, pyridaben, pyridalyl, pyrimidifen,flupyradifurone,4-[(6-Chloro-pyridin-3-ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furan-2-one(DE 102006015467), CAS: 915972-17-7 (WO 2006129714; WO2011/147953;WO2011/147952), CAS: 26914-55-8 (WO 2007020986), chlorfenapyr,pymetrozine, sulfoxaflor and pyrifluqinazon.

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in thecomposition of the invention are(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide(SSF-129),4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide,α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916,cyamidazosulfamid),3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH-7281, zoxamide),N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide(MON65500),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,acibenzolar (CGA245704) (e.g. acibenzolar-S-methyl), alanycarb,aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl,benthiavalicarb, biloxazol, bitertanol, bixafen, blasticidin S,boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim,carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396,CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon,copper containing compounds such as copper oxychloride, copperoxyquinolate, copper sulfate, copper tallate and Bordeaux mixture,cyclufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb,di-2-pyridyl disulfide 1,1′-dioxide, dichlofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim,O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole,dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyldimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos,epoxiconazole, ethirimol, ethyl-({umlaut over(Z)})—N-benzyl-N-([methyl(methyl-thioethylideneamino-oxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone (RPA407213), fenarimol,fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, fluopyram, fluoxastrobin,fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol,fluxapyroxad, folpet, fuberidazole, furalaxyl, furametpyr, guazatine,hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole,iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos,iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate,isoprothiolane, isopyrazam, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, mandipropamid, maneb, mefenoxam,metalaxyl, mepanipyrim, mepronil, metalaxyl, metconazole, metiram,metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid,oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron,penflufen, penthiopyrad, phenazin oxide, phosetyl-Al, phosphorus acids,phthalide, picoxystrobin (ZA1963), polyoxinD, polyram, probenazole,prochloraz, procymidone, propamocarb, propiconazole, propineb, propionicacid, prothioconazole, pyrazophos, pyrifenox, pyrimethanil,pyraclostrobin, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, sedaxane,sipconazole (F-155), sodium pentachlorophenate, spiroxamine,streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene,tetraconazole, thiabendazole, thifluzamid,2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram,timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole,validamycin A, vapam, vinclozolin, zineb and ziram,N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide[1072957-71-1],1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid(2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide, and1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid[2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide.

In addition, biological agents may be included in the composition of theinvention e.g. Baciullus species such as Bacillus firmus, Bacilluscereus, Bacillus subtilis, and Pasteuria species such as Pasteuriapenetrans and Pasteuria nishizawae. A suitable Bacillus firmus strain isstrain CNCM 1-1582 which is commercially available as BioNem™. Asuitable Bacillus cereus strain is strain CNCM 1-1562. Of both Bacillusstrains more details can be found in U.S. Pat. No. 6,406,690. Otherbiological organisms that may be included in the compositions of theinvention are bacteria such as Streptomyces spp. such as S. avermitilis,and fungi such as Pochonia spp. such as P. chlamydosporia. Also ofinterest are Metarhizium spp. such as M. anisopliae; Pochonia spp. suchas P. chlamydosporia.

The compounds of the invention may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

Unless otherwise stated the weight ratio of the compound of I with anadditional active ingredient may generally be between 1000:1 and 1:1000.In other embodiments that weight ratio of the compound of formula I tothe additional active ingredient may be between 500:1 to 1:500, forexample between 100:1 to 1:100, for example between 1:50 to 50:1, forexample 1:20 to 20:1, for example 1:10 to 10:1, for example 1:5 to 5:1,for example 1:1, 1:2, 1:3, 1:4, 1:5, 2:1, 3:1, 4:1, or 5:1.

Mixtures with pyrethroids, in particular pymetrozine, are of particularinterest for the present invention.

Compositions of the invention include those prepared by premixing priorto application, e.g. as a readymix or tankmix, or by simultaneousapplication or sequential application to the plant.

In order to apply a compounds of the invention as an insecticide,acaricide, nematicide or molluscicide to a pest, a locus of pest, or toa plant susceptible to attack by a pest, compounds of the invention isusually formulated into a composition which includes, in addition to thecompound of the invention, a suitable inert diluent or carrier and,optionally, a surface active agent (SFA). SFAs are chemicals which areable to modify the properties of an interface (for example,liquid/solid, liquid/air or liquid/liquid interfaces) by lowering theinterfacial tension and thereby leading to changes in other properties(for example dispersion, emulsification and wetting). It is preferredthat all compositions (both solid and liquid formulations) comprise, byweight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%,of a compound of the invention. The composition is generally used forthe control of pests such that a compound of the invention is applied ata rate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kgper hectare, more preferably from 1 g to 1 kg per hectare.

In one embodiment the compounds of the invention are used for pestcontrol on cotton at 1:500 g/ha, for example 10-70 g/ha. However, itshould be noted that due to the very damaging effect of the Anthonomusgrandis (quantity and quality on yield), sprays are often very intenseand at very low threshold levels and can be down to almost zerotolerance.

When used in a seed dressing, a compound of the invention is used at arate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

Compositions comprising a compound of the invention can be chosen from anumber of formulation types, including dustable powders (DP), solublepowders (SP), water soluble granules (SG), water dispersible granules(WG), wettable powders (WP), granules (GR) (slow or fast release),soluble concentrates (SL), oil miscible liquids (OL), ultra low volumeliquids (UL), emulsifiable concentrates (EC), dispersible concentrates(DC), emulsions (both oil in water (EW) and water in oil (EO)),micro-emulsions (ME), suspension concentrates (SC), aerosols,fogging/smoke formulations, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose envisaged and the physical, chemical andbiological properties of the compound of the invention.

Dustable powders (DP) may be prepared by mixing a compound of theinvention with one or more solid diluents (for example natural clays,kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of theinvention with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulfate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of theinvention with one or more solid diluents or carriers, one or morewetting agents and, preferably, one or more dispersing agents and,optionally, one or more suspending agents to facilitate the dispersionin liquids. The mixture is then ground to a fine powder. Similarcompositions may also be granulated to form water dispersible granules(WG).

Granules (GR) may be formed either by granulating a mixture of acompound of the invention and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound ofthe invention (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of the invention (or a solution thereof, in a suitable agent)on to a hard core material (such as sands, silicates, mineralcarbonates, sulfates or phosphates) and drying if necessary. Agentswhich are commonly used to aid absorption or adsorption include solvents(such as aliphatic and aromatic petroleum solvents, alcohols, ethers,ketones and esters) and sticking agents (such as polyvinyl acetates,polyvinyl alcohols, dextrins, sugars and vegetable oils). One or moreother additives may also be included in granules (for example anemulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof the invention in water or an organic solvent, such as a ketone,alcohol or glycol ether. These solutions may contain a surface activeagent (for example to improve water dilution or prevent crystallizationin a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of the invention in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of the invention either as a liquid(if it is not a liquid at room temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifiying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound of theinvention is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in ECs or in EWs. An ME may be either an oil-in-wateror a water-in-oil system (which system is present may be determined byconductivity measurements) and may be suitable for mixing water-solubleand oil-soluble pesticides in the same formulation. An ME is suitablefor dilution into water, either remaining as a microemulsion or forminga conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound ofthe invention. SCs may be prepared by ball or bead milling the solidcompound of the invention in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of the invention may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of the invention and a suitablepropellant (for example n-butane). A compound of the invention may alsobe dissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurized, hand-actuated spray pumps.

A compound of the invention may be mixed in the dry state with apyrotechnic mixture to form a composition suitable for generating, in anenclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerizationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of the invention and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound of theinvention and they may be used for seed treatment. A compound of theinvention may also be formulated in a biodegradable polymeric matrix toprovide a slow, controlled release of the compound.

A composition may include one or more additives to improve thebiological performance of the composition (for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of the invention).Such additives include surface active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of the invention).

A compound of the invention may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SCand DC compositions described above. Compositions for treating seed mayinclude an agent for assisting the adhesion of the composition to theseed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surfaceSFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulfuric acid (for example sodium laurylsulfate), salts of sulfonated aromatic compounds (for example sodiumdodecylbenzenesulfonate, calcium dodecylbenzenesulfonate,butylnaphthalene sulfonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol ethersulfates (for example sodium laureth-3-sulfate), ether carboxylates (forexample sodium laureth-3-carboxylate), phosphate esters (products fromthe reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulfosuccinamates, paraffin or olefine sulfonates, taurates andlignosulfonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of the invention may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapor or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of the invention may also be injected into plants or sprayedonto vegetation using electrodynamic spraying techniques or other lowvolume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often requiredto withstand storage for prolonged periods and, after such storage, tobe capable of addition to water to form aqueous preparations whichremain homogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Such aqueous preparations may containvarying amounts of a compound of the invention (for example 0.0001 to10%, by weight) depending upon the purpose for which they are to beused.

The invention will now be illustrated by the following non-limitingExamples. All citations are incorporated by reference.

BIOLOGICAL EXAMPLES

TABLE A (Ia)

Stereo- Stereo- chem- chem- istry istry X1 R1 R4 R5 at * at ** A1  3,5-methyl CH3 H R/S R dichloro- phenyl A2  3,5- 2,2,2- CH3 H R/S Rdichloro- trifluoro- phenyl ethyl A3  3,5- ethyl CH3 H S R dichloro-phenyl A4  3,5- ethyl CH3 H R/S S dichloro- phenyl A5  3,5- methyl CH3 HR/S S dichloro- phenyl A6  3,4,5- ethyl CH3 H R/S R trichloro- phenylA7  3,5- ethyl CH3 H R/S R dichloro- 4-bromo- phenyl A8  3,5- ethyl CH3H R/S R dichloro- 4-fluoro- phenyl A9  3,5- 2,2,2- CH3 H S R dichloro-trifluoro- phenyl ethyl A10 3,5- ethyl CH3 H R/S R trifluoro- methyl-4-chloro- phenyl A11 3-chloro- ethyl CH3 H R/S R 5-fluoro- phenyl A123,5- 2,2- CH3 H S R dichloro- difluoro- phenyl ethyl A13 3,4,5- 2,2,2-CH3 H S R trichloro- trifluoro- phenyl ethyl A14 3,5- 2,2,2- CH3 H S Rdichloro- trifluoro- 4-fluoro- ethyl phenyl A15 3-chloro- ethyl CH3 H SR 5-tri- fluoro- methyl- phenyl A16 3-chloro- ethyl CH3 H S R 5-bromo-phenyl A17 3-chloro- 2,2,2- CH3 H S R 5-bromo- trifluoro- phenyl ethylA18 3,5- ethyl CH3 H S R/S dichloro- phenyl A19 3,5- 2,2,2- CH3 H S R/Sdichloro- trifluoro- phenyl ethyl A20 3,5- 2,2- CH3 H S R/S dichloro-difluoro- phenyl ethyl A21 3,5- Ethyl CH3 H S R/S dichloro- 4-fluoro-phenyl A22 3,5- methyl CH3 H S R/S dichloro- phenyl A23 3,4,5- 2,2,2-CH3 H S R/S trichloro- trifluoro- phenyl ethyl A24 3,5- ethyl CH3 H S Rdichloro- 4-fluoro- phenyl A25 3,5- ethyl Cl H S R dichloro- 4-fluoro-phenyl A26 3-chloro, ethyl CH═CH—CH═CH S R 5-tri- fluoro- methyl- phenylA27 3,5- ethyl Br H S R dichloro- phenyl A28 3,5- ethyl CF3 H S Rdichloro- phenyl A29 3,4,5- ethyl CF3 H S R trichloro- phenyl A30 3-triethyl CH3 H S R fluoro- methyl- phenyl A31 3,4,5- ethyl CF3 H S Rtrichloro- phenyl A32 3,5- ethyl CF3 H S R dichloro- phenyl A33 3,4,5-ethyl Br H S R trichloro- phenyl A34 3,5- ethyl Br H S R dichloro-phenyl A35 3,4,5- ethyl CH3 H S R trichloro- phenylTable A provides compounds of formula (Ia) wherein X¹ and R¹ have thedefinitions shown below.

TABLE B (Ib)

Stereo- Stereo- chemistry chemistry X1 R1 R4 R5 at * at ** B13,5-dichloro- ethyl CH3 H R/S R phenyl B2 3,5-dichloro- ethyl CH3 H R Rphenyl B3 3,5-dichloro- 2,2,2- CH3 H R R phenyl trifluoroethylTable B provides compounds of formula (Ib) wherein X¹ and R¹ have thedefinitions shown below.

TABLE C (Ic)

Stereo- Stereo- chemistry chemistry X1 R1 R4 R5 at * at ** C13,5-dichloro- ethyl CH3 H R/S R phenyl R/S indicates a racemic mixture.Table C provides compounds of formula (Ic) wherein X¹ and R¹ have thedefinitions shown below.Nephotettix virescens (Green Leafhopper)Rice seedlings are treated with the diluted test solutions in a spraychamber. After drying, plants are infested with 10 N₅ nymphs (3replicates). 5 days after the treatment samples are checked formortality.

Application Compound Test rate/ppm Control/% A9 Nephotettix virescens(Green 200 100 leafhopper) 50 100 12 100 3 100 A3 Nephotettix virescens(Green 200 100 leafhopper) 50 100 12 100 3 90Nilaparvata lugens (Brown Plant Hopper)Rice seedlings are treated with the diluted test solutions in a spraychamber. After drying, plants are infested with 20 N₃ nymphs (2replicates). 6-12 days after the treatment samples are checked formortality

Compound Rate/ppm Control/% A1 50 98 25 93 12.5 93 A2 50 99 25 98 12.580 A3 50 100 25 100 12.5 100 A4 50 100 25 93 12.5 88 A5 50 98 25 65 12.50 A6 50 100 25 100 12.5 100 A7 50 100 25 100 12.5 100 A8 50 100 25 10012.5 100 A9 50 100 25 100 12.5 98 A10 50 100 25 100 12.5 100 A11 50 10025 55 12.5 80 A12 50 100 25 100 12.5 100 A13 50 98 25 100 12.5 75 A14 50100 25 100 12.5 100 A15 50 100 25 99 12.5 99 A16 50 98 25 97 12.5 95 A1750 100 25 100 12.5 100 A18 50 100 25 100 12.5 100 A19 50 100 25 100 12.5100 A20 50 100 25 100 12.5 100 A21 50 100 25 100 12.5 100 A22 50 100 25100 12.5 98 A23 50 100 25 98 12.5 90 A24 50 98 25 85 12.5 75 A25 50 10025 100 12.5 100 A26 50 100 25 100 12.5 83 A27 50 100 25 100 12.5 98 A2850 95 25 50 12.5 0 A29 50 100 25 88 12.5 55 A30 50 98 25 100 12.5 93 A3150 100 25 88 12.5 55 A32 50 95 25 50 12.5 0 A33 50 98 25 98 12.5 80 A3450 100 25 100 12.5 98 A35 50 98 25 100 12.5 93 B1 50 90 25 78 12.5 0 B250 88 25 70 12.5 15 B3 50 100 25 100 12.5 100 C1 50 95 25 15 12.5 0Chilo suppressalis (Rice Stem Borer)

Rice seedlings are treated and after drying the leaves are cut andtransferred into a petri dish coated with wet filter paper. 10 larvae(L2) are added and the dish is covered with a filter tissue and aplastic lid. 5 days after treatment the percentage mortality is assessed(3 replicates per concentration).

Application Compound Test rate/ppm Control/% A9 Chilo suppressalis (Ricestem 0.8 100 borer) 0.2 100 0.05 43 A3 Chilo suppressalis (Rice stem 0.8100 borer) 0.2 100 0.05 97

COMPARATIVE EXAMPLES

Compounds are tested according to the above methods. The results showthat the compounds of the invention are significantly more activeagainst the indicated rice pests than structurally similar compounds,particularly at low rates of application.

COMPARATIVE TABLE 1 Compound of the invention

Reference compound

Application rate/ Control/ Compound Test ppm % Compound of Chilosuppressalis 0.8 100  the invention (Rice stem borer) 0.2 53 ReferenceChilo suppressalis 0.8 43 compound (Rice stem borer) 0.2 23

COMPARATIVE TABLE 2 Compound of the invention

Reference compound

Appli- cation rate/ Control/ Compound Test ppm % Compound of Nilaparvatalugens 50   99 the invention (Brown plant hopper) 25   98 12.5 80Reference Nilaparvata lugens 50   45 compound (Brown plant hopper) 25   0 12.5  0The compound of the invention and reference compound are compounds B5and B4 respectively from WO 2011/067272.

1. A method comprising applying to a crop of rice plants, the locusthereof, or propagation material thereof, a compound of formula I

wherein —B¹—B²—B³— is —C═N—O—, —C═N—CH₂—, —C═CH₂—O— or —N—CH₂—CH₂—; L isa direct bond or methylene; A¹ and A² are C—H, or one of A¹ and A² isC—H and the other is N; X¹ is group X

R¹ is C₁-C₄alkyl, C₁-C₄haloalkyl or C₃-C₆cycloalkyl; R² ischlorodifluoromethyl or trifluoromethyl; each R³ is independently bromo,chloro, fluoro or trifluoromethyl; R⁴ is hydrogen, halogen, methyl,halomethyl or cyano; R⁵ is hydrogen; or R⁴ and R⁵ together form abridging 1,3-butadiene group; p is 2 or
 3. 2. A method according toclaim 1, wherein the method is a method of controlling and/or preventinginfestation of stemborer in rice comprising applying to a crop of riceplants, the locus thereof, or propagation material thereof, a compoundof formula I as defined in claim
 1. 3. A method of controlling and/orpreventing infestation of a pest chosen from at least one of a stemborerand a leaffolder in a crop of useful plants comprising applying to acrop of useful plants, the locus thereof, or propagation materialthereof, a compound of formula I as defined in claim
 1. 4. A methodaccording to claim 1, wherein the method is a method of controllingand/or preventing infestation of leaffolder in rice comprising applyingto a crop of rice plants, the locus thereof, or propagation materialthereof, a compound of formula I as defined in claim
 1. 5. (canceled) 6.A method according to claim 1, wherein the method is a method ofcontrolling and/or preventing infestation of a pest chosen from at leastone of a hopper, a gallmidge, a whorl maggot, a Rice bug, and a Blackbug in rice comprising applying to a crop of rice plants, the locusthereof, or propagation material thereof, a compound of formula I asdefined in claim
 1. 7. A method of controlling and/or preventinginfestation of a pest chosen from at least one of a hopper, a gallmidge,a whorl maggot, a Rice bug, and a Black bug in a crop of useful plantscomprising applying to a crop of useful plants, the locus thereof, orpropagation material thereof, a compound of formula I as defined inclaim
 1. 8. (canceled)
 9. (canceled)
 10. (canceled)
 11. (canceled) 12.(canceled)
 13. (canceled)
 14. (canceled)
 15. (canceled)
 16. A method oruse according to claim 1, wherein A¹ and A² are C—H, R² istrifluoromethyl, and R⁵ is hydrogen, wherein the method is a method ofcontrolling and/or preventing infestation of hoppers.
 17. A methodaccording to claim 1, wherein A¹ and A² are C—H, R² is trifluoromethyl,R⁴ is methyl, R⁵ is hydrogen, each R³ is chlorine, p is 2, wherein themethod is a method of controlling and/or preventing infestation ofhoppers or stemborer.
 18. A method according to claim 1, wherein R¹ ismethyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, trifluoroethyl,difluoroethyl, wherein the method is a method of controlling and/orpreventing infestation of hoppers or stemborer.
 19. A method accordingto claim 1, wherein R¹ is ethyl or trifluoroethyl, wherein the method isa method of controlling and/or preventing infestation of hoppers orstemborer.
 20. A method according to claim 1, wherein X¹ is3,5-dichloro-phenyl, 3,5-dichloro-4-fluorophenyl-,3,4,5-trichlorophenyl-, or 3,5-bis(trifluoromethyl)phenyl, wherein themethod is a method of controlling and/or preventing infestation ofhoppers or stemborer.
 21. A method according to claim 1, wherein—B¹—B²—B³— is —C═N—O—, wherein the method is a method of controllingand/or preventing infestation of hoppers or stemborer.
 22. A methodaccording to claim 1, wherein the compound of formula I is a mixture ofcompounds I* and I**

wherein the molar proportion of compound I** compared to the totalamount of both enantiomers is greater than 50%, wherein the method is amethod of controlling and/or preventing infestation of hoppers orstemborer.
 23. A method according to claim 1, wherein the compound offormula I is a mixture of compounds I′ and I″

wherein the molar proportion of compound I″ compared to the total amountof both enantiomers is greater than 50%, wherein the method is a methodof controlling and/or preventing infestation of hoppers or stemborer.24. A method for obtaining regulatory approval for the use of one ormore of a compound of formula I as defined in claim 1 to control insectsselected from the group consisting of stemborer, leaffolder, hoppers,Gall midge, whorl maggot, Rice bugs, and Black bugs, comprising at leastone step of referring to, submitting or relying on biological datashowing that said active ingredient reduces insect pressure.